US20050283011A1 - Process for the production of fatty acid amides - Google Patents

Process for the production of fatty acid amides Download PDF

Info

Publication number
US20050283011A1
US20050283011A1 US10/997,883 US99788304A US2005283011A1 US 20050283011 A1 US20050283011 A1 US 20050283011A1 US 99788304 A US99788304 A US 99788304A US 2005283011 A1 US2005283011 A1 US 2005283011A1
Authority
US
United States
Prior art keywords
fatty acid
oleylamide
urea
catalyst
production
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US10/997,883
Other versions
US7098351B2 (en
Inventor
Seng Hoong
Salmiah Ahmad
Hazimah Abu Hassan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Malaysian Palm Oil Board MPOB
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Assigned to MALAYSIAN PALM OIL BOARD reassignment MALAYSIAN PALM OIL BOARD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AHMAD, SALMIAH, ABU HASSAN, HAZIMAH, HOONG, SENG SOI
Publication of US20050283011A1 publication Critical patent/US20050283011A1/en
Application granted granted Critical
Publication of US7098351B2 publication Critical patent/US7098351B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines

Definitions

  • the present invention relates to a process for the production of fatty acid amides. More particularly, the present invention relates to a process for the production of fatty acid amides, particularly oleylamide, which utilises microwave irradiation as the heating element for the reaction between fatty acids and gaseous ammonia liberated by urea in the presence of a Lewis catalyst at atmospheric pressure and high temperature.
  • U.S. Pat. No. 2,013,108 describes a process of atmospheric amidation reaction, which involved passing through gaseous ammonia into the fatty acid melts that contained a surface catalyst, which was a solid inorganic substance.
  • the major drawback -for such process is that it typically requires very long reaction time that may be 48 or more hours to achieve acceptable levels of conversion and consequently some of the amide is dehydrated to the corresponding nitrile.
  • amidation process can be conducted at atmospheric pressure coupled with shorter time of reaction (11 hours); the formation of nitrile by-product is reduced.
  • the catalysts used in this process are from the Group IVb or Vb metal, preferably a compound of titanium, zirconium or tantalum.
  • U.S. Pat. No. 4,277,410 the same approach of amidation reaction is used but the catalyst employed is more specifically to alkyltin catalyst in an amount of 0.25% to 4% by weight.
  • U.S. Pat. No. 4,655,972 discloses the use of catalytic amount of hydrated oxide, preferably hydrated titanium, zirconium and tin oxide in an amount of 0.05% to 10% by weight. This process requires high. temperature which is in the range of 120° C. to 240° C. and pressure which is in the range of 100 kPa to 1000 kPa to achieve a good yield.
  • a process for the production of fatty acid amides comprises the steps of (a) combining an effective amount of fatty acid with an effective amount of a nitrogenous compound and (b) stirring and heating the mixture obtained from step (a) in a microwave oven, equipment or generator at a temperature of between 140° C. to 250° C. and at a predetermined pressure for a period of 10 to 30 minutes in the presence of a catalyst, wherein the amount of the catalyst is between 0.5 to 10 wt %.
  • the present invention relates to a process for the production of fatty acid amides. More particularly, the present invention relates to a process for the production of fatty acid amides, particularly oleylamide, which utilises microwave irradiation as the heating element for the reaction between fatty acids and gaseous ammonia liberated by urea in the presence of a Lewis catalyst at atmospheric pressure and high temperature.
  • fatty acid amides particularly oleylamide
  • microwave irradiation as the heating element for the reaction between fatty acids and gaseous ammonia liberated by urea in the presence of a Lewis catalyst at atmospheric pressure and high temperature.
  • Lewis acid catalysts 0.5 to 10 wt percent and, more preferably 0.5 to 1 wt percent Lewis acid catalysts were employed based on fatty acid weight.
  • the Lewis acid catalysts are tetra-n-butyl titanate, tetra-n-ethyl titanate and butyl tin chloride di-hydroxy.
  • the said fatty acids are preferably long carbon chain fatty acids having a chain length. of 12 to 22 carbon atoms with C18:1 as the major component.
  • the ammonia gas may come from nitrogenous compounds that can liberate gaseous ammonia upon heating such as urea and thiourea.
  • the ratio between fatty acid and urea is about 2 to 6 moles of urea per mole of fatty acid. While the process can be conducted at temperature as high as 250° C. and under high pressure, it is more preferably to carry out the process at a temperature between 160° C. to 210° C. and at atmospheric pressure.
  • the product from the reaction was subjected to solvent extraction with chloroform, after which the extraction solvent was filtered from the un-reacted urea. The solvent was then evaporated using rotary evaporator, yielding the crude fatty amide.
  • the yield of crude fatty acid amide is between 91-94% based on the weight of fatty acid.
  • the crude fatty amide was sent for HPLC analysis and based on HPLC chromatogram; the crude fatty acid amide has a purity of about 74%-76% oleylamide (93-96% conversion of oleic acid to oleylamide).
  • the crude oleylamide was subjected to purification via recrystalisation method with solvents in the following sequence, n-hexane, ethanol and acetonitrile.
  • the yield of. purified oleylamide is about 54% with 90% purity, as analysed through HPLC.
  • the improved process of this invention is particularly useful for the amidation of aliphatic monocarboxylic acids having from 12 to 22 carbon atoms.
  • Typical aliphatic acids which can be utilised in the process, are lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoliec acid, stearic acid, isostearic acid, oleic acid, linoleic acid, elaidic acid, linolenic acid, eleostearic acid, arachidic acid, behenic acid, erucic acid, lignoceric acid, nervonic acid, ricinoleic acid and the like.
  • the improvement in this process is demonstrated with oleic acid (70% purity) where the preparation of oleylamide is described.
  • the improvement in the process of this invention results from the use of microwave irradiation as the heating element in this invention.
  • the reaction time is very short and the yield of desired product is considerably high.
  • the reaction was conducted in a 900 W microwave oven and the reactants were placed in a round bottom flask and charged with catalyst.
  • the microwave oven was programmed to heat up to 195° C. from ambient room temperature within 5 minutes and this temperature was maintained for 25 minutes.
  • the reactants were stirred with the aid from a magnetic stirrer.
  • the reaction temperature will generally be about 140° C. to 210° C., however temperature as high as 230° C. can be used. As commonly known to those artisans skilled in the art, if the reaction temperature is too high, undesirable side reaction will occur, and if the temperature is too low, the reaction requires excessive time to achieve good yield. For this invention, it is preferred that the temperature be in the range of 180° C. to 200° C. Employing temperatures in this range, it is possible to achieve good conversion with minimal side product while still obtaining acceptable reaction rates.
  • microwave irradiation in this invention also permits the use of atmospheric pressure for this invention. It is particularly preferred aspect of the invention that the process of the present invention is conducted at atmospheric pressure and by such operation the use of costly high-pressure equipment is avoided.
  • a nitrogenous compound was used, which upon heating will release gaseous ammonia.
  • urea was used to generate the gaseous ammonia.
  • the amount of urea used for the process was in ratio with the amount of fatty acid, which is about 2 to 6 moles of urea, was employed per mole of fatty acid.
  • the solid urea was mixed together with the fatty acid in the reaction flask, which was then heated with the microwave irradiation until certain temperature; the urea will be melted and begin to liberate gaseous ammonia subsurface to the fatty acid. While it is not necessary to dry the urea or reactant(s), excessive amounts of water should not generally be present therein.
  • fatty amide can be produced from the reaction between fatty acid and ammonia without the present of a catalyst but the yield of fatty amide is considerably low. Therefore, in this invention a Lewis acid catalyst was employed to increase the rate of reaction between fatty acid and gaseous ammonia liberated by urea. In the process, about 0.5 to 10 wt percent and, more preferably 0.5 to 1.0 wt percent Lewis acid catalysts were employed based on fatty acid weight.
  • the Lewis acid catalysts are tetra-n-butyl titanate, tetra-n-ethyl titanate and butyl tin chloride di-hydroxy.
  • the reaction was conveniently followed by determining the acid value of the reaction mixture at the end of the reaction. It is generally desired that at the end of the reaction, the reaction mixture have an acid value of 15 or below. Using the combination of microwave irradiation and catalyst of this invention, it is possible to readily achieve acid value less than 15 in short reaction time without the formation of excessive amounts of undesirable by-product.
  • the last stage in this process is the purification of the crude oleylamide. This was done with recrystalisation method by using solvents in the following sequence, n-hexane, ethanol and acetonitrile. The ratio between each solvent and crude oleylamide. was fixed at 1 part crude oleylamide to 10 parts of solvent by weight of the crude product. In the end, the yield of purified oleylamide is about 50%-54% with 90%-95% purity, analysed through HPLC. The melting point of the oleylamide produced is in the range of 73° C.-75° C., in which, it is very close to the melting point of pure oleylamide, 74° C.-75° C.
  • Such an oleylamide is preferred for application as a mould release agent, slip agent in plastic film production, water repellent and as a raw material for cosmetics production. Following is a description by way of Examples of the process for the production of fatty acid amides.
  • Oleic acid (25 g, 74% purity) was charged into a 250 ml round bottom flask and then solid urea beads (22 g) were charged into the same flask together with tetra-n-butyl titanate (0.25 g). The mixture was stirred for a minute with a magnetic stirrer in the 900 W microwave oven cavity. The heating program raised the temperature from ambient to 190° C. in 5 minutes and the temperature was maintained at 190° C. for an additional 25 minutes. During the heating process, urea will melt at temperature above 135° C. and begin to decompose at 150° C. liberating NH 3 and CO 2 . The acid value of the reaction product was determined to be about 10 and the conversion percentage of oleic acid to reaction product based on acid value is about 95%.
  • the cooled reaction product from Example 1 was mixed with chloroform and any un-reacted urea will be filtered out from the reaction product.
  • the chloroform fraction was later evaporated by using rotary evaporator to give the crude oleylamide.
  • the yield for crude oleylamide is 92% based on the weight of oleic acid used.
  • the crude oleylamide was subjected to HPLC analysis and the chromatogram shows that the crude oleylamide has a purity of 75%. Therefore, the conversion/yield from oleic acid to oleylamide is about 93% as the starting material (oleic acid) has a purity of 74% oleic acid.
  • the crude oleylamide from Example 2 was purified by subjecting it to a series of recrystalisation. First, it was dissolved in hot n-hexane (50° C.) and the mixture was left to cool. As the mixture's temperature cooled down, oleylamide recrystalised out from the solvent. The oleylamide was filtered from the mixture with Buchner filter and then left to dry. Secondly, the recrystalised oleylamide was then dissolved in hot ethanol (50° C.) and as the mixture cooled down, impurities in the sample recrystalised from the mixture and were filtered.
  • hot ethanol 50° C.
  • the filtrate was vacuum dried and then it was dissolved in hot acetonitrile (60° C.) where the purified oleylamide recrystalised from the solvent when cooled to room temperature.
  • the yield of oleylamide from this purification process is about 54% and the purity of oleylamide produced is about 90%, while its melting point is about 75° C.
  • the same experiment was repeated by using tetra-n-ethyl titanate as the Lewis acid catalyst, while the other reaction parameters remained the same as Example 1.
  • the yield of crude oleylamide from this trial is about 94% based on the weight of oleic acid and HPLC chromatogram shows that the purity of the crude oleylamide produced is about 76%. Therefore the conversion/yield from oleic acid to oleylamide is about 96% as the starting material (oleic acid) has a purity of 74% oleic acid.
  • the same purification process was adopted and the yield is about 55%.
  • the purity of the oleylamide produced is about 95% with a melting point of 74° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

This invention discloses a rapid method of production for fatty acid amide from fatty acid and urea. One example is the preparation of oleylamide from oleic acid and urea. The yields are high and oleylamide is selectively formed by judicious choice of catalyst. The production of fatty acid amide involves heating fatty acid and urea in a microwave oven with the use of Lewis acid catalyst. The product from the reaction is subjected to solvent extraction with chloroform and then followed by purification with n-hexane, ethanol and acetonitrile via recrystalisation method. Such an oleylamide is preferred for application as a mould release agent, slip agent in plastic film production, water repellent and as a raw material for cosmetics production.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a process for the production of fatty acid amides. More particularly, the present invention relates to a process for the production of fatty acid amides, particularly oleylamide, which utilises microwave irradiation as the heating element for the reaction between fatty acids and gaseous ammonia liberated by urea in the presence of a Lewis catalyst at atmospheric pressure and high temperature.
    • BACKGROUND OF THE INVENTION
  • Numerous methods are known for the production of fatty acid amide by the reaction of corresponding fatty acid, anhydride or lower alkyl esters thereof with ammonia. These reactions can be accomplished with or without catalyst at elevated temperature and at very high pressure as described in U.S. Pat. No. 3,253,006 but the trend has been to use processes which do not require the use of high pressure and still provide high conversion with high selectivity to the desired amide product. Accordingly, catalytic procedures have been developed whereby the reaction of the fatty acids with ammonia can be achieved by substantially reduced pressures and, in some cases, even at atmospheric pressure.
  • U.S. Pat. No. 2,013,108 describes a process of atmospheric amidation reaction, which involved passing through gaseous ammonia into the fatty acid melts that contained a surface catalyst, which was a solid inorganic substance. The major drawback -for such process is that it typically requires very long reaction time that may be 48 or more hours to achieve acceptable levels of conversion and consequently some of the amide is dehydrated to the corresponding nitrile.
  • One of the competing reactions in amidation of carboxylic acids to amide is the dehydration of amide to nitrile, and this is promoted by long reaction time, therefore short reaction time is preferred in order to achieve higher yield of amide. Processes requiring shorter reaction time and employing reaction condition, which minimise undesirable by-product formation, have been developed. According to U.S. Pat. No. 3,816,483, the amidation process can be conducted at atmospheric pressure coupled with shorter time of reaction (11 hours); the formation of nitrile by-product is reduced. The catalysts used in this process are from the Group IVb or Vb metal, preferably a compound of titanium, zirconium or tantalum.
  • Furthermore, in U.S. Pat. No. 4,277,410, the same approach of amidation reaction is used but the catalyst employed is more specifically to alkyltin catalyst in an amount of 0.25% to 4% by weight. Other than that, U.S. Pat. No. 4,655,972 discloses the use of catalytic amount of hydrated oxide, preferably hydrated titanium, zirconium and tin oxide in an amount of 0.05% to 10% by weight. This process requires high. temperature which is in the range of 120° C. to 240° C. and pressure which is in the range of 100 kPa to 1000 kPa to achieve a good yield.
  • In view of starting materials for the synthesis of fatty acid amide, most commonly used raw material is the fatty acid itself, but British Patent No. GB 939378 discloses the use of long carbon chain fatty esters (C12 to C30) as the feed stock and reacting it with gaseous ammonia under high pressure and temperature. Non patent literature (Cravatt et al) revealed the use of acid halide typically the one with chlorine atom, which is more reactive compare to fatty acid and esters when react with ammonia.
  • On the other hand, most of the prior art use gaseous ammonia as starting material to react with the fatty moiety to give the desired amide. in Cravatt et al, urea and thiourea (Beckwith) are used instead of ammonia to react with fatty moiety to yield the fatty acid amide. Other than that, the U.S. Pat. No. 2,070,991 discloses the use of liquid ammonia instead of gaseous ammonia for the amidation process.
  • In general, it can be said that the usual methods have at least one of three serious drawbacks. Either the methods require long reaction time of at least 11 hours as disclosed in U.S. Pat. Nos. 4,277,410 and 4,655,972, or the methods need to be carried out at high temperature and pressure (e.g. 240° C. and 136 atm) as disclosed in U.S. Pat. No. 3,253,006, or the methods require the synthesis of an expensive intermediate compound as found in non patent literature.
  • Accordingly, it is an object of this invention to provide such a method of synthesis for normal amide of fatty acids. It is a further object of this invention to provide such a method of synthesis that will give high percentage yield of amide with a short reaction time. It is a still further object of this invention to provide such a method of synthesis that does not require the use of expensive intermediate compounds. It is another object of this invention to provide such a method of synthesis that does not require high pressure to give high percentage yield of fatty amide.
    • SUMMARY OF THE INVENTION
  • Accordingly, there is provided a process for the production of fatty acid amides, the process comprises the steps of (a) combining an effective amount of fatty acid with an effective amount of a nitrogenous compound and (b) stirring and heating the mixture obtained from step (a) in a microwave oven, equipment or generator at a temperature of between 140° C. to 250° C. and at a predetermined pressure for a period of 10 to 30 minutes in the presence of a catalyst, wherein the amount of the catalyst is between 0.5 to 10 wt %.
  • The present invention consists of certain novel features and a combination of parts hereinafter fully described and particularly pointed out in the appended claims, it. being understood that various changes in the details may be without departing from the scope of the invention, or sacrificing any of the advantage of the present invention.
    • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • The present invention relates to a process for the production of fatty acid amides. More particularly, the present invention relates to a process for the production of fatty acid amides, particularly oleylamide, which utilises microwave irradiation as the heating element for the reaction between fatty acids and gaseous ammonia liberated by urea in the presence of a Lewis catalyst at atmospheric pressure and high temperature. Hereinafter, this specification will describe the present invention according to the preferred embodiments of the present invention. However, it is to be understood that limiting the description to the preferred embodiments of the invention is merely to facilitate discussion of the present invention and it is envisioned that those skilled in the art may devise various modifications and equivalents without departing from the scope of the appended claims.
  • For the present invention, 0.5 to 10 wt percent and, more preferably 0.5 to 1 wt percent Lewis acid catalysts were employed based on fatty acid weight. Preferably the Lewis acid catalysts are tetra-n-butyl titanate, tetra-n-ethyl titanate and butyl tin chloride di-hydroxy.
  • The said fatty acids are preferably long carbon chain fatty acids having a chain length. of 12 to 22 carbon atoms with C18:1 as the major component. The ammonia gas may come from nitrogenous compounds that can liberate gaseous ammonia upon heating such as urea and thiourea. In particular, the ratio between fatty acid and urea is about 2 to 6 moles of urea per mole of fatty acid. While the process can be conducted at temperature as high as 250° C. and under high pressure, it is more preferably to carry out the process at a temperature between 160° C. to 210° C. and at atmospheric pressure.
  • The product from the reaction was subjected to solvent extraction with chloroform, after which the extraction solvent was filtered from the un-reacted urea. The solvent was then evaporated using rotary evaporator, yielding the crude fatty amide. The yield of crude fatty acid amide is between 91-94% based on the weight of fatty acid. The crude fatty amide was sent for HPLC analysis and based on HPLC chromatogram; the crude fatty acid amide has a purity of about 74%-76% oleylamide (93-96% conversion of oleic acid to oleylamide).
  • The crude oleylamide was subjected to purification via recrystalisation method with solvents in the following sequence, n-hexane, ethanol and acetonitrile. The yield of. purified oleylamide is about 54% with 90% purity, as analysed through HPLC.
  • The improved process of this invention is particularly useful for the amidation of aliphatic monocarboxylic acids having from 12 to 22 carbon atoms. Typical aliphatic acids, which can be utilised in the process, are lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoliec acid, stearic acid, isostearic acid, oleic acid, linoleic acid, elaidic acid, linolenic acid, eleostearic acid, arachidic acid, behenic acid, erucic acid, lignoceric acid, nervonic acid, ricinoleic acid and the like. The improvement in this process is demonstrated with oleic acid (70% purity) where the preparation of oleylamide is described.
  • The improvement in the process of this invention results from the use of microwave irradiation as the heating element in this invention. As a result, the reaction time is very short and the yield of desired product is considerably high. The reaction was conducted in a 900 W microwave oven and the reactants were placed in a round bottom flask and charged with catalyst. The microwave oven was programmed to heat up to 195° C. from ambient room temperature within 5 minutes and this temperature was maintained for 25 minutes. During the reaction, the reactants were stirred with the aid from a magnetic stirrer.
  • Process condition and other operational details can be widely varied. The reaction temperature will generally be about 140° C. to 210° C., however temperature as high as 230° C. can be used. As commonly known to those artisans skilled in the art, if the reaction temperature is too high, undesirable side reaction will occur, and if the temperature is too low, the reaction requires excessive time to achieve good yield. For this invention, it is preferred that the temperature be in the range of 180° C. to 200° C. Employing temperatures in this range, it is possible to achieve good conversion with minimal side product while still obtaining acceptable reaction rates.
  • The use of microwave irradiation in this invention also permits the use of atmospheric pressure for this invention. It is particularly preferred aspect of the invention that the process of the present invention is conducted at atmospheric pressure and by such operation the use of costly high-pressure equipment is avoided.
  • In this invention, a nitrogenous compound was used, which upon heating will release gaseous ammonia. In particular, urea was used to generate the gaseous ammonia. The amount of urea used for the process was in ratio with the amount of fatty acid, which is about 2 to 6 moles of urea, was employed per mole of fatty acid. The solid urea was mixed together with the fatty acid in the reaction flask, which was then heated with the microwave irradiation until certain temperature; the urea will be melted and begin to liberate gaseous ammonia subsurface to the fatty acid. While it is not necessary to dry the urea or reactant(s), excessive amounts of water should not generally be present therein.
  • It has been reported that fatty amide can be produced from the reaction between fatty acid and ammonia without the present of a catalyst but the yield of fatty amide is considerably low. Therefore, in this invention a Lewis acid catalyst was employed to increase the rate of reaction between fatty acid and gaseous ammonia liberated by urea. In the process, about 0.5 to 10 wt percent and, more preferably 0.5 to 1.0 wt percent Lewis acid catalysts were employed based on fatty acid weight. Preferably the Lewis acid catalysts are tetra-n-butyl titanate, tetra-n-ethyl titanate and butyl tin chloride di-hydroxy.
  • The reaction was conveniently followed by determining the acid value of the reaction mixture at the end of the reaction. It is generally desired that at the end of the reaction, the reaction mixture have an acid value of 15 or below. Using the combination of microwave irradiation and catalyst of this invention, it is possible to readily achieve acid value less than 15 in short reaction time without the formation of excessive amounts of undesirable by-product.
  • Separation of the reaction product was achieved by initially subjecting the product to solvent extraction with chloroform. At this stage, the fatty acid amide and un-reacted fatty acid will be extracted by the solvent, leaving behind un-reacted urea and its derivatives via filtration method. The solvent was then evaporated by using rotary evaporator, leaving behind the crude fatty acid amide. The yield of crude fatty acid amide is between 91-94% based on the weight of fatty acid. Analysis of crude fatty amide sample was achieved by using High Performance Liquid Chromatography (HPLC) method and based on HPLC chromatogram; the crude fatty acid amide has a purity of about 74%-76% oleylamide, which correspond with the purity of oleic acid (70%-80%) in the starting raw material. Therefore, the yield of oleylamide from this process is about 93%-96%.
  • The last stage in this process is the purification of the crude oleylamide. This was done with recrystalisation method by using solvents in the following sequence, n-hexane, ethanol and acetonitrile. The ratio between each solvent and crude oleylamide. was fixed at 1 part crude oleylamide to 10 parts of solvent by weight of the crude product. In the end, the yield of purified oleylamide is about 50%-54% with 90%-95% purity, analysed through HPLC. The melting point of the oleylamide produced is in the range of 73° C.-75° C., in which, it is very close to the melting point of pure oleylamide, 74° C.-75° C.
  • Such an oleylamide is preferred for application as a mould release agent, slip agent in plastic film production, water repellent and as a raw material for cosmetics production. Following is a description by way of Examples of the process for the production of fatty acid amides.
    • EXAMPLE 1
  • Oleic acid (25 g, 74% purity) was charged into a 250 ml round bottom flask and then solid urea beads (22 g) were charged into the same flask together with tetra-n-butyl titanate (0.25 g). The mixture was stirred for a minute with a magnetic stirrer in the 900 W microwave oven cavity. The heating program raised the temperature from ambient to 190° C. in 5 minutes and the temperature was maintained at 190° C. for an additional 25 minutes. During the heating process, urea will melt at temperature above 135° C. and begin to decompose at 150° C. liberating NH3 and CO2. The acid value of the reaction product was determined to be about 10 and the conversion percentage of oleic acid to reaction product based on acid value is about 95%.
    • EXAMPLE 2
  • The cooled reaction product from Example 1 was mixed with chloroform and any un-reacted urea will be filtered out from the reaction product. The chloroform fraction was later evaporated by using rotary evaporator to give the crude oleylamide. The yield for crude oleylamide is 92% based on the weight of oleic acid used. The crude oleylamide was subjected to HPLC analysis and the chromatogram shows that the crude oleylamide has a purity of 75%. Therefore, the conversion/yield from oleic acid to oleylamide is about 93% as the starting material (oleic acid) has a purity of 74% oleic acid.
    • EXAMPLE 3
  • The crude oleylamide from Example 2 was purified by subjecting it to a series of recrystalisation. First, it was dissolved in hot n-hexane (50° C.) and the mixture was left to cool. As the mixture's temperature cooled down, oleylamide recrystalised out from the solvent. The oleylamide was filtered from the mixture with Buchner filter and then left to dry. Secondly, the recrystalised oleylamide was then dissolved in hot ethanol (50° C.) and as the mixture cooled down, impurities in the sample recrystalised from the mixture and were filtered. The filtrate was vacuum dried and then it was dissolved in hot acetonitrile (60° C.) where the purified oleylamide recrystalised from the solvent when cooled to room temperature. The yield of oleylamide from this purification process is about 54% and the purity of oleylamide produced is about 90%, while its melting point is about 75° C.
    • EXAMPLE 4
  • The same experiment was repeated by using tetra-n-ethyl titanate as the Lewis acid catalyst, while the other reaction parameters remained the same as Example 1. The yield of crude oleylamide from this trial is about 94% based on the weight of oleic acid and HPLC chromatogram shows that the purity of the crude oleylamide produced is about 76%. Therefore the conversion/yield from oleic acid to oleylamide is about 96% as the starting material (oleic acid) has a purity of 74% oleic acid. The same purification process was adopted and the yield is about 55%. The purity of the oleylamide produced is about 95% with a melting point of 74° C.
    • EXAMPLE 5
  • The same experiment was repeated by using butyl tin chloride di-hydroxy as the Lewis acid catalyst, while the other reaction parameters remained the same as Example 1. The yield of crude oleylamide from this trial is about 94% based on the weight of oleic acid and HPLC chromatogram shows that the purity of the crude oleylamide produced is about 74%. Therefore the conversion/yield from oleic acid to oleylamide is about 94% as the starting material .(oleic acid) has a purity of 74% oleic acid. The same purification process was adopted and the yield is about 52%. The purity of the oleylamide produced is about 90% with a melting point of 73° C.
  • While in the foregoing specification this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein can be varied considerably without departing from the basic principles of the invention.

Claims (19)

1. A process for the production of fatty acid amides, the process comprises the steps of:
(a) combining an effective amount of fatty acid with an effective amount of a nitrogenous compound; and
(b) stirring and heating the mixture obtained from step (a) in a microwave oven, equipment or generator at a temperature of between 140° C. to 250° C. and at a predetermined pressure for a period of 10 to 30 minutes in the presence of a catalyst, wherein the amount of the catalyst is between 0.5 to 10 wt %.
2. The process as claimed in claim 1, wherein the temperature is between 160° C. to 210° C.
3. The process as claimed in claim 1, wherein the process is conducted at pressure of 1 atmosphere.
4. The process as claimed in claim 1, wherein the period of the process is between 15 to 30 minutes.
5. The process as claimed in claim 1, wherein the amount of catalyst employed is, preferably 1 wt %.
6. The process as claimed in claim 1, wherein the amides are linear primary fatty acid amides.
7. The process as claimed in claim 6, wherein the linear primary fatty acid amide is oleylamide.
8. The process as claimed in claim 7, wherein oleylamide is used as a mould release agent, slip agent in plastic film production, water repellent and as a raw material for cosmetics production.
9. The process as claimed in claim 7, wherein impurities in the oleylamide are removed via solvent extraction and recrystalisation methods.
10. The process as claimed in claim 9, wherein solvent used for solvent extraction is polar organic solvent, preferably chloroform.
11. The process as claimed in claim 9, wherein solvent used for recrystalisation is straight chain non-polar alkane, preferably n-hexane.
12. The process as claimed in claim 9, wherein solvent used for recrystalisation is polar organic solvent, preferably ethanol or acetonitrile.
13. The process as claimed in claim 1, wherein the fatty acid has a total number of carbon atoms which vary from 12 to 22, preferably 18 to 22.
14. The process as claimed in claim 13, wherein the fatty acid is from vegetable or animal fats.
15. The process as claimed in claim 1, wherein the nitrogenous compound is urea.
16. The process as claimed in claim 15, wherein the urea is technical grade urea.
17. The process as claimed in claim 1, wherein the process is either batch-wise or continuous.
18. The process as claimed in claim 1, wherein the power of the microwave oven, equipment or generator is from 100 W to 3000 W.
19. The process as claimed in claim 1, wherein the catalyst used are Lewis acids such as tetra-n-butyl titanate, tetra-n-ethyl titanate and butyl tin chloride di-hydroxy.
US10/997,883 2004-06-17 2004-11-29 Process for the production of fatty acid amides Expired - Lifetime US7098351B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI20042370 2004-06-17
MYPI20042370A MY143828A (en) 2004-06-17 2004-06-17 A process for the production of fatty acid amides

Publications (2)

Publication Number Publication Date
US20050283011A1 true US20050283011A1 (en) 2005-12-22
US7098351B2 US7098351B2 (en) 2006-08-29

Family

ID=33563069

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/997,883 Expired - Lifetime US7098351B2 (en) 2004-06-17 2004-11-29 Process for the production of fatty acid amides

Country Status (4)

Country Link
US (1) US7098351B2 (en)
JP (1) JP4928727B2 (en)
GB (1) GB2415194B (en)
MY (1) MY143828A (en)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008043493A1 (en) * 2006-10-09 2008-04-17 Clariant Finance (Bvi) Limited Method for producing fatty acid alkanol amides
WO2008043495A1 (en) * 2006-10-09 2008-04-17 Clariant Finance (Bvi) Limited Method for producing alkaline fatty acid amides
US20080289247A1 (en) * 2007-05-25 2008-11-27 Rlo Oeste, S.A. Biofuels containing nitrile moieties
DE102008017216A1 (en) * 2008-04-04 2009-10-08 Clariant International Ltd. Continuous process for the preparation of fatty acid amides
US20100076040A1 (en) * 2006-10-09 2010-03-25 Clariant Finance Wickhams Cay Method For Producing Bisbenzoxazoles
US20110083956A1 (en) * 2008-04-04 2011-04-14 Clariant Finance (Bvi) Limited Continuous Method For Producing Fatty Acid Alkanol Amides
US20110083957A1 (en) * 2008-04-04 2011-04-14 Clariant Finance (Bvi) Limited Continuous Method For Producing Amides Of Aliphatic Hydroxycarboxylic Acids
US20110089019A1 (en) * 2008-04-04 2011-04-21 Clariant Finance (Bvi) Limited Continuous Method For Producing Amides of Aromatic Carboxylic Acids
US20110089020A1 (en) * 2008-04-04 2011-04-21 Clariant Finance (Bvi) Limited Continuous Method for Producing Amides of Ethylenically Unsaturated Carboxylic Acids
US20110089021A1 (en) * 2008-04-04 2011-04-21 Clariant Finance (Bvi) Limited Method For Producing Amides In The Presence Of Superheated Water
US20110137081A1 (en) * 2008-04-04 2011-06-09 Clariant Finance (Bvi) Limited Continuous Method For Producing Amides Of Low Aliphatic Carboxylic Acids
US8067635B2 (en) 2006-10-09 2011-11-29 Clariant Finance (Bvi) Limited Method for producing tertiary amides of alkylphenyl carboxylic acids
WO2010149952A3 (en) * 2009-06-23 2012-04-19 Croda International Plc Slip and antiblocking agent
CN102557355A (en) * 2012-02-15 2012-07-11 蒋梦琪 Treatment method of wastewater containing amino compounds by copolymerization and extraction
WO2012123328A1 (en) * 2011-03-11 2012-09-20 Syngenta Limited Process for the preparation of aromatic primary amides
CN104193641A (en) * 2014-07-25 2014-12-10 南通大学 Normal pressure synthesis method of oleamide
US8974743B2 (en) 2009-06-30 2015-03-10 Clariant Finance (Bvi) Limited Device for continuously carrying out chemical reactions at high temperatures
US9000197B2 (en) 2009-09-22 2015-04-07 Clariant Finance (Bvi) Limited Continuous transesterification method
US9039870B2 (en) 2006-10-09 2015-05-26 Clariant Finance (Bvi) Limited Method for producing alkaline (meth)acrylamides
US9221938B2 (en) 2010-12-30 2015-12-29 Clariant Finance (Bvi) Limited Polymers carrying hydroxyl groups and ester groups and method for the production thereof
US9243116B2 (en) 2010-12-30 2016-01-26 Clariant International Ltd. Method for modifying polymers comprising hydroxyl groups
US9302245B2 (en) 2009-09-22 2016-04-05 Clariant International Ltd. Apparatus for continuously carrying out heterogeneously catalyzed chemical reactions at elevated temperatures
CN113372236A (en) * 2021-05-27 2021-09-10 禾大西普化学（四川）有限公司 Method for preparing fatty acid amide by adopting pulse type static rigid-flexible mixer
CN115466193A (en) * 2022-10-14 2022-12-13 禾大西普化学（四川）有限公司 Method for preparing long-chain fatty acid amide by microwave method

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4941971B2 (en) * 2007-01-29 2012-05-30 独立行政法人産業技術総合研究所 Process for producing alkylthio-substituted nitrogen-containing heterocyclic compound
KR101678461B1 (en) * 2016-04-18 2016-11-22 이창호 Method and apparatus for manufacturing carboxylic acid amide compound
US10676658B2 (en) 2017-08-15 2020-06-09 Saudi Arabian Oil Company Oil-based drilling fluids for high pressure and high temperature drilling operations
US10876039B2 (en) 2017-08-15 2020-12-29 Saudi Arabian Oil Company Thermally stable surfactants for oil based drilling fluids
US10870788B2 (en) 2017-08-15 2020-12-22 Saudi Arabian Oil Company Thermally stable surfactants for oil based drilling fluids
US10647903B2 (en) 2017-08-15 2020-05-12 Saudi Arabian Oil Company Oil-based drilling fluid compositions which include layered double hydroxides as rheology modifiers and amino amides as emulsifiers
US10745606B2 (en) 2017-08-15 2020-08-18 Saudi Arabian Oil Company Oil-based drilling fluid compositions which include layered double hydroxides as rheology modifiers
US10640696B2 (en) 2017-08-15 2020-05-05 Saudi Arabian Oil Company Oil-based drilling fluids for high pressure and high temperature drilling operations
US10793762B2 (en) 2017-08-15 2020-10-06 Saudi Arabian Oil Company Layered double hydroxides for oil-based drilling fluids
US10988659B2 (en) 2017-08-15 2021-04-27 Saudi Arabian Oil Company Layered double hydroxides for oil-based drilling fluids

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2013108A (en) * 1932-07-06 1935-09-03 Ig Farbenindustrie Ag Production of carboxylic amides
US2070991A (en) * 1934-05-14 1937-02-16 Shell Dev Process for the production of acid amides
US3253006A (en) * 1962-10-09 1966-05-24 Procter & Gamble Preparation of amides of higher fatty acids
US3816483A (en) * 1970-06-02 1974-06-11 Henkel & Cie Gmbh Carboxylic acid amide preparation
US4277410A (en) * 1980-05-02 1981-07-07 Emery Industries, Inc. Process for the production of carboxylic amides using alkyltin catalysts
US4655972A (en) * 1983-07-04 1987-04-07 Internationale Octrooi Maatschappij "Octropa" B.V. Catalytic preparation of carbonamides

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3069677B2 (en) * 1996-07-25 2000-07-24 工業技術院長 Method for producing organic carboxylic acid ester compound
JP3586707B2 (en) * 1996-07-25 2004-11-10 独立行政法人産業技術総合研究所 Method for producing acid amide or acid imide compound

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2013108A (en) * 1932-07-06 1935-09-03 Ig Farbenindustrie Ag Production of carboxylic amides
US2070991A (en) * 1934-05-14 1937-02-16 Shell Dev Process for the production of acid amides
US3253006A (en) * 1962-10-09 1966-05-24 Procter & Gamble Preparation of amides of higher fatty acids
US3816483A (en) * 1970-06-02 1974-06-11 Henkel & Cie Gmbh Carboxylic acid amide preparation
US4277410A (en) * 1980-05-02 1981-07-07 Emery Industries, Inc. Process for the production of carboxylic amides using alkyltin catalysts
US4655972A (en) * 1983-07-04 1987-04-07 Internationale Octrooi Maatschappij "Octropa" B.V. Catalytic preparation of carbonamides

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9039870B2 (en) 2006-10-09 2015-05-26 Clariant Finance (Bvi) Limited Method for producing alkaline (meth)acrylamides
WO2008043495A1 (en) * 2006-10-09 2008-04-17 Clariant Finance (Bvi) Limited Method for producing alkaline fatty acid amides
WO2008043493A1 (en) * 2006-10-09 2008-04-17 Clariant Finance (Bvi) Limited Method for producing fatty acid alkanol amides
US8101785B2 (en) 2006-10-09 2012-01-24 Clariant Finance (Bvi) Limited Method for producing fatty acid alkanol amides
US8067635B2 (en) 2006-10-09 2011-11-29 Clariant Finance (Bvi) Limited Method for producing tertiary amides of alkylphenyl carboxylic acids
US20100010244A1 (en) * 2006-10-09 2010-01-14 Clariant Finance (Bvi)Limited Method For Producing Fatty Acid Alkanol Amides
US20100076040A1 (en) * 2006-10-09 2010-03-25 Clariant Finance Wickhams Cay Method For Producing Bisbenzoxazoles
US20100116642A1 (en) * 2006-10-09 2010-05-13 Clariant Finance (Bvi) Limited Method For Producing Alkaline Fatty Acid Amides
US8067612B2 (en) 2006-10-09 2011-11-29 Clariant Finance (Bvi) Limited Method for producing bisbenzoxazoles
US8956425B2 (en) 2007-05-25 2015-02-17 Rio Oeste, S.A. Biofuels containing nitrile moieties
US20080289247A1 (en) * 2007-05-25 2008-11-27 Rlo Oeste, S.A. Biofuels containing nitrile moieties
WO2009121487A1 (en) * 2008-04-04 2009-10-08 Clariant International Ltd Continuous method for producing fatty acid amides
EA020190B1 (en) * 2008-04-04 2014-09-30 Клариант Финанс (Бви) Лимитед Continuous method for producing fatty acid amides
US20110137081A1 (en) * 2008-04-04 2011-06-09 Clariant Finance (Bvi) Limited Continuous Method For Producing Amides Of Low Aliphatic Carboxylic Acids
US20110089020A1 (en) * 2008-04-04 2011-04-21 Clariant Finance (Bvi) Limited Continuous Method for Producing Amides of Ethylenically Unsaturated Carboxylic Acids
US20110083956A1 (en) * 2008-04-04 2011-04-14 Clariant Finance (Bvi) Limited Continuous Method For Producing Fatty Acid Alkanol Amides
US20110089019A1 (en) * 2008-04-04 2011-04-21 Clariant Finance (Bvi) Limited Continuous Method For Producing Amides of Aromatic Carboxylic Acids
DE102008017216A1 (en) * 2008-04-04 2009-10-08 Clariant International Ltd. Continuous process for the preparation of fatty acid amides
US20110083957A1 (en) * 2008-04-04 2011-04-14 Clariant Finance (Bvi) Limited Continuous Method For Producing Amides Of Aliphatic Hydroxycarboxylic Acids
EA020190B9 (en) * 2008-04-04 2015-03-31 Клариант Финанс (Бви) Лимитед Continuous method for producing fatty acid amides
US20110092722A1 (en) * 2008-04-04 2011-04-21 Clariant Finance (Bvi) Limited Continuous Method For Producing Fatty Acid Amides
US20110089021A1 (en) * 2008-04-04 2011-04-21 Clariant Finance (Bvi) Limited Method For Producing Amides In The Presence Of Superheated Water
DE102008017216B4 (en) * 2008-04-04 2013-08-14 Clariant International Ltd. Continuous process for the preparation of fatty acid amides
CN101910114B (en) * 2008-04-04 2014-06-04 科莱恩金融(Bvi)有限公司 Continuous process for the preparation of fatty acid amides
US8884040B2 (en) * 2008-04-04 2014-11-11 Clariant Finance (Bvi) Limited Continuous method for producing fatty acid amides
CN102596895A (en) * 2009-06-23 2012-07-18 禾大国际股份公开有限公司 Slip and antiblocking agent
WO2010149952A3 (en) * 2009-06-23 2012-04-19 Croda International Plc Slip and antiblocking agent
CN102596895B (en) * 2009-06-23 2014-09-17 禾大国际股份公开有限公司 Slip and antiblocking agent
US9328307B2 (en) 2009-06-23 2016-05-03 Croda International Plc Branched acids
US8865809B2 (en) 2009-06-23 2014-10-21 Croda International Plc Slip and antiblocking agent
US8974743B2 (en) 2009-06-30 2015-03-10 Clariant Finance (Bvi) Limited Device for continuously carrying out chemical reactions at high temperatures
US9302245B2 (en) 2009-09-22 2016-04-05 Clariant International Ltd. Apparatus for continuously carrying out heterogeneously catalyzed chemical reactions at elevated temperatures
US9000197B2 (en) 2009-09-22 2015-04-07 Clariant Finance (Bvi) Limited Continuous transesterification method
US9243116B2 (en) 2010-12-30 2016-01-26 Clariant International Ltd. Method for modifying polymers comprising hydroxyl groups
US9221938B2 (en) 2010-12-30 2015-12-29 Clariant Finance (Bvi) Limited Polymers carrying hydroxyl groups and ester groups and method for the production thereof
WO2012123328A1 (en) * 2011-03-11 2012-09-20 Syngenta Limited Process for the preparation of aromatic primary amides
CN102557355A (en) * 2012-02-15 2012-07-11 蒋梦琪 Treatment method of wastewater containing amino compounds by copolymerization and extraction
CN104193641A (en) * 2014-07-25 2014-12-10 南通大学 Normal pressure synthesis method of oleamide
CN113372236A (en) * 2021-05-27 2021-09-10 禾大西普化学（四川）有限公司 Method for preparing fatty acid amide by adopting pulse type static rigid-flexible mixer
CN115466193A (en) * 2022-10-14 2022-12-13 禾大西普化学（四川）有限公司 Method for preparing long-chain fatty acid amide by microwave method

Also Published As

Publication number Publication date
GB2415194B (en) 2008-10-08
MY143828A (en) 2011-07-15
JP2006096736A (en) 2006-04-13
JP4928727B2 (en) 2012-05-09
GB0426052D0 (en) 2004-12-29
GB2415194A (en) 2005-12-21
US7098351B2 (en) 2006-08-29

Similar Documents

Publication Publication Date Title
US7098351B2 (en) Process for the production of fatty acid amides
EP0339882A1 (en) Process for the production of lactide
CN115286514B (en) Preparation method of 4' -chloro-2-aminobiphenyl sulfate
KR20170016754A (en) New method for preparation of chromanone derivatives
CA2777158A1 (en) Process for preparing a phenylalanine derivative
KR960001913B1 (en) Process for the preparation of 3-cyano-4-aryl-pyrroles
EP1588998B1 (en) A process for the preparation of 2-chloro-3-(phenylmethoxy)propionic acid potassium salt
EP2307354B1 (en) Process for preparing a benzoylbenzeneacetamide derivative
RU1836348C (en) Method for obtaining higher alkyl ethers of (4-amino-3,5-dichloro-6-fluoro-2-pyridinyloxy) acetic acid
US5646317A (en) Processes for the preparation of N-(long-chain acyl)amino acid and salt thereof, and intermediate amidonitrile and process for the preparation thereof
CN109734656A (en) A kind of preparation method of nitrendipine
KR101894091B1 (en) New method for preparation of chromanone derivatives
US5659081A (en) Process for the preparation of cyclopropanecarboxamide
JP2001278867A (en) Production of cyclic acids
JPS6121229B2 (en)
EP1911739A2 (en) Crystalline form of (S)-2-phenylethylammonium (R)-diphenyl-methanesulphinyl-acetate
DE60127455T2 (en) PROCESS FOR PREPARING BETA-KETONITRILE COMPOUNDS
US7425648B2 (en) Process for the preparation of nateglinide, preferably in B-form
US6953859B2 (en) Production process for 5-alkyl-oxazolidin-2,4-dione
JP2552319B2 (en) 3-amino-2,4,5-trifluorobenzoic acid
US5756839A (en) Process for preparing D,L-aspartic acid from ammonium salts of the maleic acid
EP0985658A1 (en) Process for producing l-valine benzyl ester p-toluenesulfonate
US6242646B1 (en) Method of producing 2,4-dichloro-5-hydroxyacetanilide
US5206369A (en) Process for the dehydration of dihydroxypiperidinedicarboxylates
JPS6147825B2 (en)

Legal Events

Date Code Title Description
AS Assignment

Owner name: MALAYSIAN PALM OIL BOARD, MALAYSIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HOONG, SENG SOI;AHMAD, SALMIAH;ABU HASSAN, HAZIMAH;REEL/FRAME:016310/0583;SIGNING DATES FROM 20050114 TO 20050115

STCF Information on status: patent grant

Free format text: PATENTED CASE

CC Certificate of correction
FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAT HOLDER CLAIMS SMALL ENTITY STATUS, ENTITY STATUS SET TO SMALL (ORIGINAL EVENT CODE: LTOS); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

REFU Refund

Free format text: REFUND - PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: R1552); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

FPAY Fee payment

Year of fee payment: 8

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2553)

Year of fee payment: 12